CN102000813B - Integrated metal processing facility and method - Google Patents
Integrated metal processing facility and method Download PDFInfo
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- CN102000813B CN102000813B CN2010105006557A CN201010500655A CN102000813B CN 102000813 B CN102000813 B CN 102000813B CN 2010105006557 A CN2010105006557 A CN 2010105006557A CN 201010500655 A CN201010500655 A CN 201010500655A CN 102000813 B CN102000813 B CN 102000813B
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D11/00—Process control or regulation for heat treatments
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D11/00—Process control or regulation for heat treatments
- C21D11/005—Process control or regulation for heat treatments for cooling
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/0068—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for particular articles not mentioned below
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B9/00—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
- F27B9/14—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment
- F27B9/20—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment the charge moving in a substantially straight path
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B9/00—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
- F27B9/30—Details, accessories or equipment specially adapted for furnaces of these types
- F27B9/40—Arrangements of controlling or monitoring devices
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D19/00—Arrangements of controlling devices
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D21/00—Arrangement of monitoring devices; Arrangement of safety devices
- F27D21/0014—Devices for monitoring temperature
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/84—Controlled slow cooling
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- Furnace Details (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Tunnel Furnaces (AREA)
- Heat Treatments In General, Especially Conveying And Cooling (AREA)
- Control Of Heat Treatment Processes (AREA)
- Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
- Control Of Temperature (AREA)
Abstract
A integrated facility for forming and heat treating a metal casting is provided, the facility comprising: a pouring station for pouring a molten metal into a mold to form a casting; a process temperature control station downstream from said pouring station, said process temperature control station comprising a temperature sensing device in a heat treatment furnace; wherein said the temperature sensing device and said heat source are adapted to maintain the temperature of the casting at or above a process control temperature for the metal of the casting, and wherein upon receipt of a rejection signal from said temperature sensing device, said transfer mechanism removes the casting prior to entry into said furnace.
Description
The application is that 200580024668.9 entering State Period date is that the international filing date on January 22nd, 2007 is denomination of invention the dividing an application for the application for a patent for invention of " integrated metal processing facility " on June 1st, 2005 for applicant's application number.
Background technology
Traditionally, in the conventional method that forms metal casting, for example have the metal die of inner chamber or the mold of sand mo(u)ld and be full of motlten metal, said inner chamber portion has within it defined the external structure of hoping foundry goods.The core of qualification foundry goods internal structure holds or is placed in the mold, when motlten metal solidifies around core, forms the interior details of foundry goods.After the motlten metal of foundry goods solidified, foundry goods moved to usually to handle in the stove and carries out heat treating castings, removes the sand of core and/or mold, and other essential processing.The metal or metal alloy of heat treatment processes condition foundry goods is to obtain to be used for the desired physical properties of given application.
Usually, be transported to the process of heat treatment station from the cast station at foundry goods, if particularly allow foundry goods to place considerable time, foundry goods can be exposed in the external environment of casting or metal-working plant.As a result, foundry goods is easy to begin quick cooling from fusing or semi-molten temperature.Although need foundry goods cooling to a certain degree so that casting solidification; But casting temperature descends manyly more; The time that foundry goods remains under the casting process critical-temperature (also be called technological temperature control) is long more, is heated to required heat treatment temperature and foundry goods is heat-treated the needed time foundry goods long more.For example, it has been found that for the metal of some type, foundry goods is reduced to each minute below the control of its technological temperature, the result that all need realize hoping at least about four minutes additional heat treatment time.Therefore, even reduce under the technological temperature control of foundry goods metal shortly 10 minutes, also need additional heat treatment time of about at least 40 minutes could obtain the physical property of hope.Therefore, for the thermal effectiveness that obtains to hope, these foundry goods needed heat treatment 2-6 hour at least usually, and in some cases the time longer.This causes more energy to be used, and therefore causes higher heat treatment cost.
Summary of the invention
In brief, the present invention generally include a kind of to the foundry goods that forms from metal or metal alloy pour into a mould, the integrated metal processing facility of shaping, heat treatment and other processing.This integrated metal processing facility generally includes the cast station, and at this motlten metal of aluminium or iron for example, or metal alloy is cast in mold or the mould, in for example nonvolatil metal mold, semi-permanent mold or the sand mold.Then, said mold moves to transfer position from the cast or the casting position of cast station, from its mold, takes out or is transported on the heat-treatment production line at this foundry goods.Said connecting gear generally includes robots arm, crane, overhead elevator or lift, push rod, conveyer belt or similar connecting gear.Same mechanism also can be used for from mold, taking out foundry goods and foundry goods is sent on the heat-treatment production line.From pouring into a mould station to transfer position and/or to the course of conveying of heat-treatment production line, the motlten metal in the foundry goods can be cooled to be enough to form the degree of foundry goods this.
Said heat-treatment production line or thermal treatment unit generally include technological temperature control station and heat treatment station or heat-treatment furnace, and said heat-treatment furnace has one or more furnace chamber usually, and optional, has the quench station that is usually located at the heat treatment station downstream.Said technological temperature control station is generally elongated chamber or passage, before foundry goods gets into heat treatment station, receives foundry goods through said chamber or passage.Said chamber can comprise a series of thermals source, for example the heating element heater of pharoid, infrared, induction, convection current, conduction or other types.The wall of said technological temperature control station also can comprise radiative material with the top, and when foundry goods and/or mold moved through said chamber, these materials were usually towards said foundry goods and/or mold radiation or guiding heat.Alternatively, can use a series of thermals source, comprise radiant heater element, the thermal source of for example infrared and inductive heating element, convection current, conduction or other types is to direct into foundry goods or mold with heat at foundry goods or mold when the cast station is sent to heat treatment station.In addition, can heating element heater or thermal source directly be installed on the connecting gear with heating foundry goods and/or sand mold.
When foundry goods and/or the mold that wherein has a foundry goods when passing technological temperature control station, the cooling of foundry goods is limited in technological temperature control or this is more than temperature.Technological temperature is controlled the normally required following temperature of solution heat treatment temperature of foundry goods metal; Thereby make foundry goods be cooled to be enough to quantity or the degree that they are solidified; But under this temperature, foundry goods is elevated to its solution heat treatment temperature and subsequently the required time of heat treating castings is increased by index law.Foundry goods remains on its technological temperature control or this temperature is above till said foundry goods gets into heat treatment station.
Through stoping the foundry goods cooling and foundry goods being remained under the control of basic technology temperature or this temperature more than temperature of foundry goods metal, the needed time of heat treating castings can obviously reduce.Therefore, the output quantity of casting pouring station can increase, and like this, the whole machining process of foundry goods and heat treatment time can reduce.
Before getting into heat-treatment furnace, foundry goods passes through the inlet region.Casting temperature comes under observation to confirm whether temperature reduces to preset or below the predetermined discharge temperature.If casting temperature is equal to or less than discharge temperature, can use any proper device that foundry goods is taken away from heat-treatment production line.If foundry goods is acceptable, it just advances to and is used for heat treated heat-treatment furnace.
Thermal treatment unit can include the structure that helps take away and/or reclaim core and/or mold.Thereafter, the processing that foundry goods can add, for example, quenching, Ageing Treatment and/or other heat treatment.
For a person skilled in the art, after the detailed description of having read below in conjunction with accompanying drawing, each purpose of the present invention, feature and advantage will be more obvious.
Description of drawings
Figure 1A is the sketch map of the illustrative metal system of processing of the various aspects according to the present invention;
Figure 1B is the sketch map of another illustrative metal system of processing of various aspects according to the present invention, has shown collection and conveying from a plurality of cast stations to the foundry goods of thermal treatment unit;
Fig. 1 C is the sketch map of another illustrative metal system of processing of various aspects according to the present invention, wherein from mold, takes out the cooling thing;
Fig. 1 D is another example system of the various aspects according to the present invention, has shown the connecting gear that comprises heater;
Fig. 2 A is the illustrative processes temperature control station of the various aspects according to the present invention and the top plan view of heat treatment station;
Fig. 2 B is the lateral elevational view of control station of technological temperature shown in Fig. 2 A and heat treatment station;
Fig. 3 is the perspective view of the exemplary batch process system of various aspects according to the present invention;
Fig. 4 A and 4B have shown according to the present invention the illustrative processes temperature control station of various aspects, comprise source of conductive heating;
Fig. 5 A and 5B have shown according to the present invention another illustrative processes temperature control station of various aspects, comprise direct heat source/impact (impingement) thermal source; And
Fig. 6 A and 6B have shown according to the present invention another illustrative processes temperature control station of various aspects, comprise radiant heat source.
The specific embodiment
At length with reference to accompanying drawing, identical in the accompanying drawings Reference numeral is represented identical parts now.Figure 1A-3 schematically shows the method for integrated metal processing facility or system 5 and processing metal foundry goods.Metal casting technique is normally known in those skilled in the art, only briefly describes traditional casting technique from reference purpose below.Those skilled in the art will appreciate that the present invention can be used for the casting technique of any kind, comprise being used to be shaped the metal of aluminium, iron, steel and/or other types and the metal casting technique of metal alloy castings.Therefore, the present invention and not should not only limit to use with the metal or metal alloy of particular cast technology or particular type.
Shown in Figure 1A, motlten metal or metal alloy M are poured in mould or the mold 10 to form foundry goods 12 at cast station or casting station 11 usually, for example, and cylinder head, engine body or similar foundry goods.The core of being processed by the organic bond of sand and for example phenolic resins 13 holds or is placed in the mold 10, thereby produces cavity and/or foundry goods details or core print in the foundry goods.Alternatively, each mold can be nonvolatil mold or mould, and usually by metal, for example steel, cast iron or other materials known in the art are processed.This mold can have clamshell type design, so that open and therefrom take out foundry goods.Still alternatively; Said mold can be " precision sand " formula mold and/or " greensand mold ", these molds usually by with adhesive, for example phenolic resins or other binding agents known in the art sand material of mixing; For example silica sand or zircon sand are processed, and are similar to sand core 13.Said mold also can comprise semi-permanent sand mold, and it has outside mold wall usually, and this wall is processed by sand and binding material, the metal of for example steel or the combination of two kinds of materials.
Should be understood that; Term " mold " is generally used for referring to above-mentioned all types of mold hereinafter; Comprise nonvolatil or metal die, semi-permanent and precision sand formula mold and other metal molds, but point out except the situation of particular type mold.It is to be further understood that; In following each embodiment; Only if pointed out the mold and/or the Technology for Heating Processing of particular type, otherwise the present invention can be used for the foundry goods that from permanent mold, takes out is heat-treated, or the foundry goods that still remains in the sand mold is heat-treated so that the heat treatment of making up; And the destruction sand mold, reclaim sand.
Shown in Figure 1A, each mold 10 generally includes sidewall 14, upper wall or top 16, lower wall or bottom 17, and these walls have formed internal cavities 18 jointly, and motlten metal is contained in this cavity and forms foundry goods 12.Cast gate 19 forms on the upper wall of each mold or top 16 usually and is communicated with internal cavities, is used for making the deposite metal pass through each mold and getting into internal cavities 18 pouring into a mould station 11 places.Shown in Figure 1A-1C, cast station 11 generally includes casting bag or the kindred organization 21 that is used for motlten metal M is poured into mold.Said cast station 11 also comprises conveyer belt 22; For example disc type conveyer belt, piston, calibration structure or similarly connecting gear; One or more mold is moved to point of delivery or position 24 from cast or casting position 23; Wherein at the pouring position poured with molten metal in mold, foundry goods is taken out from its mold or the mold that will wherein have a foundry goods is transported on thermal treatment unit 26 or the heat-treatment production line from the cast station at transfer position.After motlten metal had been poured in the mold, mold was sent to transfer position, and wherein, degree that metal is cooled to hope in the required mould of metal or temperature are to solidify the formation foundry goods.Foundry goods is heat-treated under the heat treatment temperature of hope subsequently.
It has been found that; When the foundry goods metal cools off; It reaches here temperature or the temperature range that is called " technological temperature control " or " technology critical-temperature ", is lower than this temperature, and casting temperature is elevated to heat treatment temperature and heat-treats all significantly increases of required time.Those of ordinary skill in the art should be appreciated that size and dimension and many other factors of special metal that the technological temperature control of the foundry goods that is used for being handled by the present invention will be used according to foundry goods and/or metal alloy, foundry goods change.
On the one hand, technological temperature control is about 400 ℃ for some alloys or metal.On the other hand, technological temperature control can be approximately 400-600 ℃.On the other hand, technological temperature control can be approximately 600-800 ℃.On the other hand, technological temperature control can be approximately 800-1100 ℃.On the other hand, technological temperature is controlled for some alloys or metal, and for example iron can be approximately 1000-1300 ℃.In a particular instance, aluminium/copper alloy can have about 400-470 ℃ technological temperature control.In this example, technological temperature control is being used under the solution heat treatment temperature of most of copper alloys usually, and said solution heat treatment temperature typically is about 475-495 ℃.Although particular instance provided herein should be appreciated that size and dimension and many other factors of the special metal that uses according to foundry goods and/or metal alloy, foundry goods, technological temperature control can be any temperature.
When the metal of foundry goods was in the desired process temperature controlling range, that kind that foundry goods typically is cooled to be enough to according to hope was solidified.Yet; If allow the foundry goods metal to be cooled to it below technological temperature control; It has been found that the foundry goods metal cooled off 1 minute below technological temperature control, foundry goods just needs about at least 4 minutes of extra-heated to reach the heat treatment temperature of hope; For example for aluminium/copper alloy being about 475-495 ℃, perhaps is about 510-570 ℃ for aluminum/magnesium alloy.Therefore, even foundry goods very short time of cooling under its technological temperature control, suitably and up hill and dale the needed time of the said foundry goods of heat treatment also can be significantly elongated.In addition; Will be appreciated that; In the batch process system that in for example Figure 1B, 1C and 1D, shows, wherein several foundry goods are handled in a collection of through heat treatment station, are used for the heat treatment time of foundry goods by the gross has minimum temperature usually based on this batch the required heat treatment time of foundry goods.Therefore; If one of foundry goods that is processed in this batch is cooled to be lower than it below technological temperature control, for example, continue about 10 minutes; Usually need by the gross, the for example extra heat treatment that continues at least 40 minutes is to guarantee that all foundry goods are by suitably also heat treatment up hill and dale.
Therefore, many aspects of the present invention relate to integrated treatment facility or system 5 (Figure 1A-Fig. 3) and the method for handling metal casting.Said each system is designed so that (be positioned at its mold or separate with mold) foundry goods moves and/or be sent to heat treatment system or unit 26 from casting station 11; Make technological temperature control or this that the cooling of motlten metal reaches metal more than temperature simultaneously, but the heat treatment temperature of being less than or equal to its hope is to allow casting solidification.Therefore, many aspects of the present invention comprise that the system that is used to keep watch on casting temperature is to guarantee that foundry goods roughly remains on technological temperature control or this is more than temperature.For example, thermoelectricity occasionally other similar temperature sensing device or system can be placed on the said foundry goods, or contiguous this foundry goods places, or is placed on from the casting station to the interval location of the foundry goods mobile route of heat-treatment furnace so that roughly continuous supervision to be provided.Alternatively, can adopt and confirm as the enough frequent time interval and carry out periodicity and keep watch on.This device can link to each other with thermal source, and like this, temperature measuring or sensing device and thermal source can cooperate with the temperature with foundry goods and roughly remain on the technological temperature control of foundry goods metal or this is more than temperature.Should be clear; Casting temperature can be measured by an ad-hoc location on foundry goods or in the foundry goods; Perhaps can be through the mean temperature of measuring on the foundry goods or the temperature of a plurality of positions in the foundry goods calculates, any other mode that is perhaps required according to application-specific or that hope be measured.Therefore, for example, casting temperature can foundry goods on or a plurality of positions in foundry goods measure, and the minimum temperature of surveying, the maximum temperature of surveying, the medium temperature of surveying, the equal temperature of institute's lining or its any combination or variation possibly calculated or confirm as to the total moisture content value.
In addition, before getting into heat-treatment furnace, foundry goods can pass inlet or discharge area 110, and wherein the temperature of each foundry goods obtains keeping watch on to confirm whether this foundry goods need has been cooled to too much energy temperature to be brought up to the degree of heat treatment temperature.The inlet region can be included in the technological temperature control station, perhaps can be the zone that separates, as pointing out usually in institute's drawings attached.Casting temperature can pass through any suitable TEMP or measurement mechanism, and for example thermocouple is kept watch on to confirm whether casting temperature has reached or drop to below the preset or predetermined discharge temperature.On the one hand, the said predetermined discharge temperature temperature that can be the foundry goods metal below the technological temperature control (for example, approximately 10-20 ℃).In yet another aspect, the temperature of (for example, about 10-20 ℃) below the heat treatment temperature that said predetermined discharge temperature can be heat-treatment furnace or baking oven.If foundry goods has been cooled to be equal to or less than predetermined temperature, said control system can send and discharges signal to transmitting or remove mechanism.In response to the detection of defect situation or signal, this foundry goods can be identified so that further assessment perhaps can be taken off from transmitting production line.Foundry goods can pass through any suitable mechanism or device, includes but not limited to that robots arm or other automatics are taken away, and perhaps said foundry goods can manually be taken away by the operator.
As stated; Should be clear; Casting temperature can be measured by an ad-hoc location on foundry goods or in the foundry goods; Perhaps can be through the mean temperature of measuring on the foundry goods or the temperature of a plurality of positions in the foundry goods calculates, any other mode that is perhaps required according to application-specific or that hope be measured.Therefore, for example, casting temperature can be measured a plurality of positions on foundry goods or in the foundry goods, and the minimum temperature of surveying, the maximum temperature of surveying, the medium temperature of surveying, the equal temperature of institute's lining or its any combination or variation possibly calculated or confirm as to total value.
In Figure 1A and 2A-2B, first embodiment that shows integrated equipment 5 and be used for moving and/or processing the technology of foundry goods.Figure 1B and 3 also shows integrated equipment 5 and shaping and handles additional, the optional embodiment of the technology of foundry goods, and its medium casting is collected and processed through heat treatment in batch processing formula device.Yet, those skilled in the art will appreciate that principle of the present invention goes for batch-type and the single continuous processing type equipment through said equipment of foundry goods equally.Therefore, following embodiment and not should not only limit to continuously or the process equipment of batch-type.Fig. 1 C and 1D also show the optional embodiment that is used to carry out additional procedure of processing of the present invention, for example, remove cooling thing (Fig. 1 C) or foundry goods is transported to (Fig. 1 D) a plurality of heat-treatment furnaces from foundry goods.In addition, those skilled in the art will appreciate that that discuss and each structure embodiment illustrated in the accompanying drawings of hereinafter can be combined to form additional embodiment of the present invention.
In the embodiment shown in Figure 1A and the 2A-2B, carrying or pouring into a mould station 11 foundry goods 12 is taken out from its mold 10 through connecting gear 27.Shown in Fig. 2 A and 2B; Induction system or mechanism 27 generally include robots arm or crane 28; Yet it will be appreciated by those skilled in the art that; Can use the various other systems and the device that move foundry goods and/or mold, for example overhead system elevator or lift, conveyer belt, push rod or other materials similar carrying mechanisms.Shown in Figure 1A, 1B and 2A; Robots arm 28 generally includes and is used to engage or joint or grip portion or the clamp 29 and the pedestal 31 of clamping mold or foundry goods; Robots arm 28 is rotatably installed on the said pedestal, thereby can between point of delivery 24 of pouring into a mould station and heat-treatment production line, shown in arrow 32 and 32 ' (Fig. 2 A), move.In addition, shown in Figure 1B, connecting gear can be used for from a plurality of cast stations 11 and 11 ' transfer molds and/or foundry goods, and can said mold and/or foundry goods be transported to a plurality of heat-treatment production lines or unit 26 (Fig. 1 C).
Usually, the mold that inside has a foundry goods moves to from cast station 11 and picks up or point of delivery 24 (Fig. 2 A), and wherein connecting gear 27 picks up the mold that its inside accommodates foundry goods usually, or from its mold, takes out foundry goods 12 and foundry goods 12 is transported to thermal treatment unit 26.Like this, same operator or connecting gear can be used for taking out foundry goods from the cast station, and foundry goods is sent into thermal treatment unit.Usually, thermal source or heating element heater 33 are adjacent to point of delivery 28 settings to foundry goods heat to be provided.Said thermal source can comprise the heating element heater or the thermal source of any kind usually, for example conduction, radiation, infrared, convection current and the direct thermal source of impingement.Shown in Fig. 2 A, can use a plurality of thermals source 33, it is positioned in from the course of conveying of cast station heat treated production line to foundry goods heat supply efficiently.
Usually, under the situation of permanent or metal die or mold, mold is opened at the point of delivery place, and takes out foundry goods through connecting gear, shown in Fig. 1 D.Then, said connecting gear is transported to foundry goods on one or more inlet conveyer belt 34 (Figure 1B and 2A) of thermal treatment unit, production line or system 26 of integrated process equipment 5.When mold is opened and take out foundry goods; Along with foundry goods is transported to thermal treatment unit and makes foundry goods be exposed to the external environment of Foundry Works; Thermal source 33 (Fig. 2 A) directly applies heat to foundry goods; Stop or otherwise control the cooling of foundry goods, thereby the technological temperature that can make foundry goods roughly remain on the foundry goods metal controls or this is more than temperature.
Processing for the foundry goods of processing in semipermanent or the sand mold; Usually remain in its mold at the heat treatment process medium casting; During this period; The thermal degradation of the binder material through keeping the mold sand destroys mold, and the whole mold that connecting gear 27 will wherein accommodate foundry goods is transported to inlet conveyer belt 34 from point of delivery.Therefore, thermal source 33 will continue to apply heat to mold itself, and the heat that is applied is controlled so that the casting temperature in the mold maintains technological temperature control or this of foundry goods metal roughly more than the temperature, and can not cause mold excessively or too early to disintegrate.
Hereinafter, when mentioning conveying, heating, handling or other modes move or when processing foundry goods,, take out and processing foundry goods itself and do not have their mold otherwise be appreciated that this argumentation comprises only if point out in addition; And foundry goods remains on heat-treating process in the sand mold, and the destruction of mold and core, and the recovery of sand are like United States Patent(USP) No. 5; 294,994, No.5,565; 046, No.5,738,162; No.6,217,317 and the U.S. Patent application No.09/665 that submits in 9 days September in 2000 of not concluding; The U.S. Patent application No.10/051 that submitted on January 18th, 354 and 2002, disclosed content in 666, its content is incorporated herein by reference in this integral body.
Shown in Figure 1A and 2A-2B, foundry goods begins by inlet conveyer belt 34 (Fig. 2 A and 2B), or conveyer belt 34 and 34 ' (Figure 1B) calibration or be sent to preset chamber or technological temperature is controlled in workshop section or the module 36.Shown in Fig. 2 A and 2B; Technological temperature control station or module generally include the inner chamber 37 of heating; Its medium casting and/or its inside have the mold of foundry goods on chain conveyor, roller or similar connecting gear 38, pass through inner chamber 37 along its processing delivery pathways along heat-treatment production line.Foundry goods at the upper reaches or arrival end 39 get into chambers 37, and leave chamber 37, and directly send in the heat-treatment furnace or station 42 of heat-treatment production line 26 usually through the downstream or the port of export 41.The entrance and exit end 39 and 41 of technological temperature control station also can be opened, and maybe can comprise door or similar enclosed construction, shown in mark 43 among Fig. 2 B, thereby to help sealed chamber 37 to avoid too much thermal loss.Usually, foundry goods is directly sent into heat treatment station 42 from technological temperature control station 36, and wherein, heat treatment and technological temperature control station link together, and have further avoided potential thermal loss, if desired, also allow to divide equally heat.
Fig. 4 A-6B shows the multiple various embodiment of technological temperature control station.Fig. 4 A-4B illustrates the technological temperature control station 36 that comprises convection thermal source 45.Each source of conductive heating generally includes the nozzle or the air blast 51 of one or more medium source that is connected in heating through conduit 52.In this respect, air blast 51 arrange or the roof 47 that is positioned chamber 37 and sidewall 46 around, thereby can make the medium of heating, for example air or other gas and/or fluid import in the chamber, and import facing to being contained in its inner foundry goods and/or mold.What said convection blowers tended to produce around the foundry goods disturbance usually adds hot fluid stream, as shown in arrow 53, so that heat is applied on all sides of foundry goods and/or sand mold basically.As a result, casting temperature roughly remains on the technological temperature control of foundry goods metal or this is more than temperature.In addition; When foundry goods carries out in its sand mold under the situation of processed, control the heat that applies in the station at technological temperature and be used for heated mold, its temperature is elevated to decomposes or ignition temperature; Under this temperature, binder material wherein takes fire, pyrolysis or otherwise separate.
On the other hand, air blast or nozzle 52 are positioned at the front of the technological temperature control station of contiguous its arrival end, under higher speed and/or temperature, move, so that stop the cooling of foundry goods and/or mold quickly.Towards the middle part and/or the end of chamber, for example the nozzle or the air blast 52 of the outlet location of technological temperature control station can move under lower temperature and speed, thereby avoid sand mold to degrade fully, allow casting solidification simultaneously.
Alternatively, Fig. 5 A and 5B show technological temperature control station 36 ' another embodiment, one or more pharoid 54 of thermal source 45 ' comprise usually wherein, for example infrared heating element, electromagnetic-energy or similarly radiant heating source.On the one hand, pharoid 54 can be around the sidewall and roof 46 and 47 of the radiant chamber 37 of technology controlling and process station 36, is arranged in a plurality of positions or is arranged on the position and orientation of hope, for example, is similar to the layout of convection blowers 51.The same with convection heat sources 52, when foundry goods gets into technological temperature control station, can under higher temperature, move more promptly to stop the cooling of foundry goods in the sand mold near the pharoid of chamber arrival end.In addition, vacuum blower, pump or exhaust fans/systems 56 can be connected in radiant chamber in radiant chamber 37, to produce negative pressure through conduit 57.Like this, can in chamber, extract the heat and/or the waste gas of the binding agent burning generation of core and/or sand mold out, thereby avoid the pharoid element over-temperature.
Technological temperature control station 36 has been shown " another embodiment, wherein show direct impingement heat source 45 " in Fig. 6 A and 6B.This direct impingement heat source comprises and a series ofly is arranged in burner or nozzle 58 on select locations in the radiant chamber 37 or the orientation with group or array way.These burners 58 are connected in fuels sources through conduit 59 usually, for example natural gas etc.Directly the nozzle or the burner element of impingement heat source roughly apply heat towards sidewall, top and the bottom of foundry goods.Therefore, foundry goods is heated full and uniformly, and the sand material that therefrom discharges can also expose with direct heating, so that with its binder material after-flame.
Those skilled in the art will appreciate that these different thermals source can make up use in radiant chamber.And a plurality of chambers can be connected and used to stop the cooling of foundry goods more than the temperature in technological temperature control or this, before foundry goods gets into heat treatment station, keep casting temperature thereafter.
On the other hand, the waste gas that produces during casting molten metal can the introducing technology temperature radiant chamber of control station 36, as shown in arrow 60 so that can from the process of heating of metal foundry goods, divide equally heat and recover energy.On the other hand; Because the unnecessary heat that binding agent destruction in the heat treatment station 42 in foundry goods core and/or the sand mold and burning and heat treating castings produce also can turn back to technological temperature control station; Shown in the dotted arrow among Figure 1A 61, control the internal environment of the radiant chamber of station to help the heating process temperature.The recovery of this waste gas and heat help to reduce the chamber that technological temperature is controlled station be heated to hope or essential temperature to stop the required energy of foundry goods cooling through chamber.
In addition, shown in Fig. 2 B, 4A, 5A and 6A, along the bottom formation collection funnel or the skewed slot 62 of technological temperature control station 36, it is positioned under the radiant chamber 37.This funnel 62 is usually included in the downward-sloping sidewall 63 in its lower end 64.When binding agent began thermal degradation in technological temperature control station, said sloped sidewall was collected the sand that comes off in foundry goods core and/or the sand mold.Sand flows to downwards on the collection conveyer belt 66 under the open lower end that is positioned at funnel 62 usually.Usually place fluidization system or mechanisms 67 along the bottom 64 of the wall of funnel 62.This fluidizer generally includes burner, air blast, distributor or similar fluidisation unit, for example, and at United States Patent(USP) No. 5,294; 994, No.5,565,046; No.5, open and require protection in 738,162, its content is hereby incorporated by; Wherein with the MEDIA FLOW of heating, for example air or other fluids join in the sand, impel adhesive further to degrade; Thereby the cake broke that helps to make the sand that comes off from foundry goods and binding agent to form, so that reclaim the sand of core and/sand mold, making foundry goods is pure form.The sand that reclaims is collected on the conveyer belt 66, and transmits and leave technological temperature control station.
In addition; Shown in Figure 1A, 2A, 2B, 4A, 5A and 6A; Waste gas is used for unnecessary heat that the burning of foundry goods core and/or sand mold binder material produces with also can be collected or extraction from the radiant chamber 37 of technological temperature control station 36; And import heat treatment station 42, shown in the arrow among Figure 1A 68.Unnecessary heat and waste gas lead to heat treatment station from technological temperature control station makes the heat that in the chamber of technological temperature control station, produces to reclaim, and sand mold and/or binder degradation of sand cores produce waste gas in thermal processing chamber continuation heating and/or burning.Shown in Figure 1A, air blast or similarly air distribution mechanism 69 further installed usually along heat treatment station, and usually will be in the heat treatment process of foundry goods and the waste gas that produces of the binder material after-flame process of the core of foundry goods and/or sand mold extract out.These waste gas are collected by air blast, and usually import to these waste gas further handle and the incinerator 71 of burning in, thereby these waste gas are handled again, and reduce the amount of pollutants that foundry goods and Technology for Heating Processing cause.Can also use filter to filter the waste gas that comes from technological temperature control station, and/or filter the gas from the heat treatment station to the incinerator to take a step forward in waste gas entering heat treatment station.
Therefore; Said technological temperature control station is as heat treatment station or the preceding embedding zone of chamber; Wherein when foundry goods wait for to get into heat treatment station, foundry goods can be maintained at or be limited in technological temperature control or this more than temperature, but is lower than required heat treatment temperature.Therefore, said system can make casting production line move with faster or more effective speed, and foundry goods needn't be waited in line to send in the heat treatment station being exposed to external environment following time, thereby causes foundry goods to be cooled to below their the technological temperature control.After this, these foundry goods can be independent, like Figure 1A, shown in 1C and the 2A-2B, or in batch, shown in Figure 1B, 1C and 3, is transported in the heat treatment station 42 and heat-treats, and makes said core and/or sand mold breakdown and removal, and reclaim sand in some cases.
Heat treatment station 42 (Fig. 2 B) can be elongated stove, comprises the furnace chamber 75 that one or more is installed continuously, and conveyer belt 76 extends through said furnace chamber to carry foundry goods.Thermal source 77 (Fig. 2 A) comprises the source of conductive heating of the heat medium that applies air for example or other fluids; For example air blast or nozzle; Conduction heat sources, fluid bed for example, induction, radiation and/or other types thermal source can be installed in the wall and/or roof of chamber 75; Be used in various degree with around the foundry goods of quantity heat and optional air-flow being provided, thereby foundry goods is heated to suitable heat treatment temperature.The heat treatment temperature of this hope and heat treatment time will change according to the type of the metal or metal alloy that forms foundry goods, and this is as well known to those skilled in the art.
The instance of the various heat-treatment furnaces that are suitable for using together with the present invention is included in United States Patent(USP) No. 5,294, and 994, No.5,565,046 and No.5, those heat-treatment furnaces shown in 738,162, its content is hereby incorporated by.The heat-treatment furnace that uses with the present invention or another instance of station are open and be shown in United States Patent(USP) No. 6; 217; 317, the U.S. Patent application No.09/665 that submitted on September 9th, 2000; The U.S. Patent application No.10/051 that submitted on January 18th, 354 and 2002, in 666, its content all is incorporated herein by reference at this.This heat treatment station or stove can comprise the structure that is recovered in during the heat treating castings from the sand of core and/or molds dislodged.
After the heat treatment, foundry goods takes out from heat treatment station usually and moves to quench station 78 (Figure 1A), is used for cleaning and further processing.Said quench station generally includes has cooling fluid, and for example the quenching tank of water or other known coolant maybe can comprise the chamber with series of spray nozzles, said nozzle ejection cooling fluid, for example air, water or similar cooling medium.Then, taking out foundry goods further cleans as required and handles.
Another embodiment of integrated equipment 5 has been shown in Figure 1B.This equipment 5 comprises the connecting gear 27 that is shown as crane or robots arm 28, its with foundry goods from a plurality of pouring product lines or station 11 and 11 ' take off.In this example, said pouring product line or station 11 and 11 ' be shown as the carrousel type system, wherein mold can rotation between cast or casting position 23 and point of delivery 24.Connecting gear 27 engages and carries its inside to have the sand mold of foundry goods, or with foundry goods from mold, takes out and with foundry goods be transported to one or more conveyer belt 34 and 34 that enters the mouth of thermal treatment unit 26 '.These foundry goods can move into and pass through technological temperature control station 36 individually and introduce in the heat treatment station 42, maybe can collect in the basket bucket or in the delivery tray 79, are used for the batch processing foundry goods.
In the example system shown in Figure 1B 5, technological temperature control station 36 forms the elongated radiation pipeline 81 that has defined chamber 82 usually, and the sand mold that foundry goods or its inside accommodate foundry goods can pass through this chamber and move or transmit.Radiation pipeline 81 comprises a series of thermals source 83 along its installation, the multiple different heat sources of for example describing 45,45 above with reference to the embodiment of Fig. 2 A-2B and 4A-6B ' and 45 ".Usually, the wall 84 and the roof of the chamber 82 of radiation pipeline 81 are processed or are coated with refractory material by refractory material, make the heat that in radiation pipeline, produces towards foundry goods reflection and/or radiation.Foundry goods can be collected and/or leave in basket bucket 79 or be arranged in the similar delivery tray of the collection station 86 of radiation pipeline 81 ends.This basket bucket 79 or pallet are used to hold foundry goods and/or the mold through heat treatment station 42.Foundry goods is collected in the radiant chamber or the passage that are used in the basket bucket in that foundry goods is controlled station 36 through technological temperature alternatively and before carries out batch processing in heat treatment station, shown in Fig. 1 C and 3.
In Fig. 1 C, schematically show another embodiment of integrated equipment 5 of the present invention.In this embodiment, technological temperature control station 36 is shown as elongate radiation pipeline or chamber 81 (as said to Figure 1B), connects or sends into the cooling thing and remove station 87.This cooling thing removal station 87 links to each other with heat treatment station 42 and foundry goods is sent in the heat treatment station 42.Usually, said foundry goods moves and heat treatment or processing in remaining in semipermanent or sand mold the time, and wherein said sand mold also comprises " the cooling thing " that is installed in wherein.The metallic plate normally processed by steel or similar material of cooling thing has the design shape (relief) of the required project organization that is used to form cast(ing) surface, and when the casting molten metal material or before this, will cool off thing and put into mold.Therefore, before heat treating castings, must take out the cooling thing, or reclaim said cooling thing and reuse.After passing through the chamber 82 of radiation pipeline 81, during this period, the burning of sand mold will begin usually at least in part, and the cooling thing can take out easily, and can obviously not incur loss through delay moving of mold and foundry goods heat treated station 42.After removing chill removal station at the cooling thing, there is the mold of foundry goods directly to send into heat treatment station usually in it and heat-treats, core and sand mold breakdown, and reclaim sand.
Another embodiment of integrated equipment of the present invention has been shown in Fig. 1 D.In this embodiment, foundry goods can from mold, take out and be transported to usually the inlet conveyer belt 90 or 91 be used for directly sending into one or more heat-treatment furnace or station 92.Alternatively, if foundry goods forms in sand mold, then whole mold can be transported on one of inlet conveyer belt 90 or 91 from point of delivery 28.Shown in Fig. 1 D, foundry goods takes out from mold and carries foundry goods subsequently, or the mold that its inside accommodates foundry goods takes out and be transported to heat treatment station 92 from the cast station, and this can be accomplished by same connecting gear or operator usually.
In this embodiment, thermal source 93 is installed on the connecting gear 27, when foundry goods moves to the inlet conveyer belt 90 of heat-treatment furnace 92 or one of 91 the time, this thermal source directly applies heat to foundry goods and/or sand mold from the point of delivery of casting production line.As stated, said thermal source can comprise radiation energy, for example infrared or electromagnetic launcher, induction, convection current and/or conduction heat sources, or the thermal source of conspicuous other types for a person skilled in the art.When foundry goods or mold are transported to the inlet conveyer belt; Come from the heat guiding foundry goods of the thermal source 93 that is installed on the connecting gear 27 or one or more surface of mold; For example top and/or side; Therefore thereby can stop the cooling of foundry goods and/or mold, the temperature of foundry goods metal remained essentially in the technological temperature control of this metal or this is more than temperature.
Fig. 3 has shown another embodiment of the present invention.In this example, foundry goods and/or sand mold can be placed directly in through connecting gear 27 and collect in basket bucket or the delivery tray 100, and are transported to and are used for process of thermal treatment temperature control station in batches.In this device; Foundry goods 12 is packed in a series of cabins or chamber 101 of delivery tray 100 usually, and its medium casting is placed on known indexing position, gets into and through technological temperature control station 102 during with heat treatment station 103 with convenient foundry goods; Can directly apply the heat of decoring or other functions; Like the U.S. Patent application No.09/665 that submitted on September 9th, 2000,354 is disclosed and the requirement protection, and its content is hereby incorporated by.In this embodiment, when foundry goods was packed into, the common calibration of pallet 100 got into and leave the chamber 104 of technological temperature control station, as arrow 106 and 106 ' shown in.As a result, the exposure of foundry goods in external environment minimized, simultaneously in each other cabin 101 of pallet remaining foundry goods in this batch is housed, the exposure in boundary's environment outside of its medium casting will make foundry goods be cooled to that technological temperature is controlled or critical-temperature under.
In addition, as shown in Figure 3, can also directed thermal source 107 be provided for each cabin 101 of pallet 100.For example, when first cabin 101 ' in foundry goods 12 ' and calibration when getting into technological temperature control station 102 is housed, the foundry goods and/or the sand mold guiding heat of first thermal source 107 ' to being arranged in specific cabin.Then, when follow-up foundry goods or mold were packed other chambers or the cabin of basket bucket into, the additional heating source 107 in these cabins of leading was started working.Therefore, the heating of the chamber 104 of the technological temperature control station specific region that can be limited in as required or lead is so that more effectively heat foundry goods.
As shown in Figure 3, a series of air blasts or other similar air moving device 108 can be installed to the top of technological temperature control station, are used to extract out the waste gas of core and/or sand mold binder material degraded generation.Subsequently, gas and used heat import heat treatment station 103 through conduit 109, carry out heat recovery and pollution abatement, and help avoid combustible waste and gather at the side and the top of technological temperature control station 102 chambers.
Therefore, it should be appreciated by those skilled in the art that according to the detailed description of preceding text, the present invention has application widely.Under the situation that does not break away from the present invention's essence and scope, the of the present invention many remodeling except here describing, and many variations, modification and equivalent arrangements will become obvious or reasonable through the present invention and above-mentioned detailed description.
Invention has been described although be directed against particular aspects here, should be appreciated that just the present invention's explanation and exemplary of this detailed description, and just from providing abundant openly the object of the invention to make.The detailed description of here setting forth both had been not used in restriction the present invention and had not also got rid of any other this type embodiment of the present invention, remodeling, distortion, modification and equivalent arrangements, and the present invention only is limited to accompanying claims and equivalence is described.
Claims (6)
1. integrated equipment that is used to form with the heat-treated metal foundry goods, this equipment comprises:
The cast station is used for poured with molten metal to mold to form foundry goods;
Connecting gear;
Be positioned at the technological temperature control station in said cast station downstream, said technological temperature control station comprises the temperature sensing device that links to each other with connecting gear with thermal source; With
Be positioned at the heat-treatment furnace in said technological temperature control station downstream, said heat-treatment furnace also includes oral region;
Wherein, said temperature sensing device and said thermal source are suitable for cooperating as required heat being imposed on foundry goods, thereby before foundry goods gets into heat-treatment furnace, casting temperature are remained on the technological control temperature of foundry goods metal or this is more than technological control temperature; With
Wherein, When the temperature of the foundry goods that detects the said inlet region that gets into heat-treatment furnace through said temperature sensing device is lower than exhaust temperature, sends the discharging signal and said connecting gear was removed foundry goods before foundry goods is heat-treated through said heat-treatment furnace from said temperature sensing device.
2. integrated equipment as claimed in claim 1; Wherein said technological temperature control station also comprises the controller that links to each other with said thermal source with said temperature sensing device, and said controller is controlled the heat that imposes on foundry goods with the technological control temperature that casting temperature remained on the foundry goods metal or this is more than technological control temperature.
3. integrated equipment as claimed in claim 1, wherein said connecting gear receives the discharging signal 10 ℃-20 ℃ the time at casting temperature below following temperature:
(a) technological control temperature of foundry goods metal, wherein said technological control temperature is a temperature, at this below temperature, the every reduction of casting temperature one minute, the additional heat treatment time that just need carry out at least four minutes to be reaching the foundry goods character of hope, or
(b) temperature of heat-treatment furnace.
4. the method for formation and heat treatment foundry goods, this method comprises:
With poured with molten metal in the mold to form foundry goods;
When foundry goods is kept watch on casting temperature when the cast station is transported to heat-treatment furnace;
Casting temperature and the predetermined exhaust temperature kept watch on are compared,, before foundry goods gets into said heat-treatment furnace, discharge said foundry goods if said temperature is equal to or less than said exhaust temperature;
Wherein, said exhaust temperature is the temperature that is lower than the predetermined technological control temperature of foundry goods metal or is lower than the heat treatment temperature of heat-treatment furnace;
If the temperature of keeping watch on is greater than exhaust temperature; The monitor temperature and the technological control temperature of foundry goods are compared; If said temperature is lower than said technological control temperature, apply as required heat give foundry goods with before getting into heat-treatment furnace at foundry goods with the temperature maintenance of foundry goods at technological control temperature or be higher than technological control temperature;
Foundry goods is put into heat-treatment furnace; With
Said foundry goods is heat-treated.
5. method as claimed in claim 4; Wherein, Said exhaust temperature is below the technological control temperature of foundry goods metal 10 ℃-20 ℃, and wherein said technological control temperature is a temperature, at this below temperature; The every reduction of casting temperature one minute, the additional heat treatment time that just need carry out at least four minutes is to reach the foundry goods character of hope.
6. method as claimed in claim 4, wherein, said exhaust temperature is below the heat treatment temperature of heat-treatment furnace 10 ℃-20 ℃.
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US57610704P | 2004-06-02 | 2004-06-02 | |
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CN200580024668.9A Division CN101001963B (en) | 2004-06-02 | 2005-06-01 | Integrated metal processing facility |
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CN102000813B true CN102000813B (en) | 2012-07-25 |
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CN200580024668.9A Expired - Fee Related CN101001963B (en) | 2004-06-02 | 2005-06-01 | Integrated metal processing facility |
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CA2436749C (en) * | 2001-02-02 | 2011-11-29 | Consolidated Engineering Company, Inc. | Integrated metal processing facility |
US20080236779A1 (en) * | 2007-03-29 | 2008-10-02 | Crafton Scott P | Vertical heat treatment system |
DE102010009118B4 (en) * | 2009-10-19 | 2017-04-20 | Audi Ag | Process for the heat treatment of castings |
JP5890183B2 (en) * | 2012-01-17 | 2016-03-22 | 本田技研工業株式会社 | Solution furnace |
US9757800B2 (en) | 2012-08-24 | 2017-09-12 | Jeffrey D. Eagens | Transportation of castings produced in and still encapsulated in its green sand mold producing enhanced casting cooling and processed sand properties with subsequent high velocity controlled air cooling of the castings |
DE102012218159B4 (en) | 2012-10-04 | 2018-02-08 | Ebner Industrieofenbau Gmbh | handling device |
WO2015033311A1 (en) * | 2013-09-06 | 2015-03-12 | Disa Industries A/S | Method of operating a metal foundry, system for performing the method, and metal foundry comprising the system |
AU2016254028B2 (en) | 2015-04-28 | 2019-10-17 | Consolidated Engineering Company, Inc. | System and method for heat treating aluminum alloy castings |
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- 2005-06-01 CN CN2010105006557A patent/CN102000813B/en not_active Expired - Fee Related
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- 2005-06-01 CN CN200580024668.9A patent/CN101001963B/en not_active Expired - Fee Related
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EP1766100B1 (en) | 2012-08-08 |
CN102000813A (en) | 2011-04-06 |
CN101001963A (en) | 2007-07-18 |
CN101001963B (en) | 2015-08-19 |
MXPA06014028A (en) | 2007-08-14 |
EP2319945A2 (en) | 2011-05-11 |
JP5689403B2 (en) | 2015-03-25 |
EP2319945B1 (en) | 2013-03-13 |
EP2319945A3 (en) | 2011-11-16 |
JP2008501860A (en) | 2008-01-24 |
JP2014073531A (en) | 2014-04-24 |
WO2005121386A3 (en) | 2006-03-16 |
JP5575365B2 (en) | 2014-08-20 |
JP2012040614A (en) | 2012-03-01 |
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KR20070024675A (en) | 2007-03-02 |
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